Synergistic sono-adsorption and adsorption-enhanced sonochemical degradation of dyes in water by additive manufactured PVDF-based materials

The present study proposes the first mechanistic model accounting for the most meaningful physico-chemical phenomena taking place in liquid phase adsorption processes under ultrasound. Initially, this study was aimed at developing an easy-to-make and easy-to-recover piezocatalyst for the degradation of RhB in water by combining the high piezocatalytical performance of BaTiO(3) with a compatible piezoelectric support such as PVDF, manufactured by a customised additive manufacturing – direct ink writing system with in-situ poling. However, initial results showed that the resulting PVDF-BaTiO(3) composite slabs performed worse than BaTiO(3) piezocatalysts on their own, and that poling did not have any effect on their performance (82% RhB removal after 2 h when using either poled or unpoled PVDF-BaTiO(3) composite slabs compared to 92% RhB removal after 2 h in presence of BaTiO(3) piezocatalysts). Further investigation with pure PVDF materials demonstrated that, instead of piezocatalysis, synergistic ultrasound-assisted adsorption and sonochemical degradation were taking place, enabling the removal of >95% of the dye within 40 min of ultrasound treatment in the presence of 4 g L(–1) of additive manufactured PVDF slabs. The results of this study and their evaluation with the mechanistic model proposed for liquid phase adsorption under ultrasound suggest that the adsorption of RhB on additive manufactured PVDF slabs was enhanced by the structure, higher specific surface ratio and higher volume of mesopores achieved through the 3D-printing process, as well as the minimisation of film resistance to mass transport due to ultrasound. Moreover, adsorption on additive manufactured PVDF enhanced the sonochemical degradation of the dye due to its high concentration in the adsorbed phase. This study demonstrates that adsorption processes, especially in the presence of PVDF materials, may be significantly more important in piezocatalysis than what has been reported to date, to the point that the synergistic combination of sono-adsorption and sonochemical degradation in presence of additive-manufactured PVDF slabs may be enough to achieve high removal rates of dyes in water.